CN102674523A - Method for recycling ammonia and nitrogen in waste watery by aid of chemicrystallization - Google Patents
Method for recycling ammonia and nitrogen in waste watery by aid of chemicrystallization Download PDFInfo
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- CN102674523A CN102674523A CN2012101640275A CN201210164027A CN102674523A CN 102674523 A CN102674523 A CN 102674523A CN 2012101640275 A CN2012101640275 A CN 2012101640275A CN 201210164027 A CN201210164027 A CN 201210164027A CN 102674523 A CN102674523 A CN 102674523A
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- ammonia
- magnesium ammonium
- pyrolysis
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 64
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 59
- 238000004064 recycling Methods 0.000 title abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 title abstract description 4
- 239000002699 waste material Substances 0.000 title 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 111
- 229910052567 struvite Inorganic materials 0.000 claims abstract description 92
- 238000000197 pyrolysis Methods 0.000 claims abstract description 91
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims abstract description 90
- 239000002351 wastewater Substances 0.000 claims abstract description 86
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 7
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 60
- 239000000047 product Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 16
- 239000003929 acidic solution Substances 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000413 hydrolysate Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims 2
- 239000003814 drug Substances 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract 3
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 17
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 16
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 description 13
- YJGHGAPHHZGFMF-UHFFFAOYSA-K magnesium;sodium;phosphate Chemical compound [Na+].[Mg+2].[O-]P([O-])([O-])=O YJGHGAPHHZGFMF-UHFFFAOYSA-K 0.000 description 11
- 238000009395 breeding Methods 0.000 description 8
- 230000001488 breeding effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 238000004939 coking Methods 0.000 description 6
- 239000003337 fertilizer Substances 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 239000002894 chemical waste Substances 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 4
- 150000003016 phosphoric acids Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- GISGYEHPOAIOTM-UHFFFAOYSA-L [O-]P([O-])(O)=O.OP(O)(O)=O.N.N.N.[Mg+2] Chemical compound [O-]P([O-])(O)=O.OP(O)(O)=O.N.N.N.[Mg+2] GISGYEHPOAIOTM-UHFFFAOYSA-L 0.000 description 2
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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Abstract
The invention discloses a method for recycling ammonia and nitrogen in waste water by the aid of chemicrystallization, and belongs to the field of waste water treatment. The method includes (1) adding sodium hydroxide powder into magnesium ammonium phosphate solid, performing pyrolysis to obtain a pyrolysis product; (2) feeding the pyrolysis product obtained in the step (1) into the waste water to obtain magnesium ammonium phosphate crystal sediment; (3) recycling the magnesium ammonium phosphate crystal obtained in the step (2), drying the magnesium ammonium phosphate crystal, feeding sodium hydroxide powder into the magnesium ammonium phosphate crystal, carrying out heating pyrolysis, and feeding a pyrolysis product into the waste water to obtain the ammonia by means of circulating sedimentation; and (4) feeding the pyrolysis product obtained in the step (3) into acidic liquor to carry out acid pyrolysis once after the step (1), the step (2) and the step (3) are carried out twice and five times, and feeding an acid pyrolysis product into the waste water to obtain ammonia by means of circulating sedimentation. By the aid of the method, the problem of over high medicament cost of a magnesium ammonium phosphate method is solved, and the difficult problem that ammonia and nitrogen removal rate is reduced along with increase of ammonia circulating sedimentation frequency of magnesium ammonium phosphate is also solved.
Description
Technical field
The invention belongs to field of waste water treatment, more particularly, is a kind of high-concentration ammonia nitrogenous wastewater circulation process method, can efficiently remove the ammonia nitrogen in the waste water, is applicable to high-concentration ammonia nitrogenous wastewaters such as handling fertilizer industry.
Background technology
In recent years, the heavy ammonia process of ammoniomagnesium phosphate crystal has obtained extensive studies.The ammoniomagnesium phosphate crystal method is to form the purpose that the magnesium ammonium phosphate crystal reaches the removal ammonia nitrogen through the ammonia nitrogen that in high-concentration ammonia nitrogenous wastewater, adds in magnesium salts and phosphoric acid salt and the waste water.Magnesium ammonium phosphate is that good slow release is fertile, and when removing ammonia nitrogen in waste water, precipitated product also can carry out recycling.Yet reagent cost is too high to be a difficult point of this method research.
To the too high difficult problem of reagent cost, Chinese scholars has proposed new terms of settlement.The document of delivering mainly contains: " the Ammonium nitrogen removal from coking wastewater by chemical precipitation recycle technology " that Tao Zhang etc. delivered in " Water Research " 43 phases in 2009; " the Removal of nutrients from piggery wastewater using struvite precipitation and pyrogenation technology " that Haiming Huang etc. delivered in " Bioresource Technology " 102 phases in 2011.This type of technology mainly is to circulate through the magnesium ammonium phosphate pyrolysis product to reach the effect that reduces reagent cost; Release the ammonia rate in order to improve the magnesium ammonium phosphate pyrolytic; In the magnesium ammonium phosphate pyrolytic process, added sodium hydroxide solution, improve the release of ammonia nitrogen in the magnesium ammonium phosphate pyrolytic process.In " Ammonium nitrogen removal from coking wastewater by chemical precipitation recycle technology " that Tao Zhang etc. 2009 delivered in " Water Research " 43 phases, at OH
-:
Mol ratio is 2:1, and pyrolysis temperature is 110 ℃, and when pyrolysis time was 3 h, magnesium ammonium phosphate ammonia nitrogen release rate surpassed 90%.Yet pyrolysis product and excessive water vapor form phosphoric acid salt magnesium (Dittmarite) in the magnesium ammonium phosphate pyrolytic process, and phosphoric acid salt magnesium is the same with magnesium ammonium phosphate; Finally resolve into secondary magnesium phosphate; But phosphoric acid salt magnesium is more stable than magnesium ammonium phosphate performance, and required pyrolysis temperature is higher, and pyrolysis time is longer.Therefore, in the magnesium ammonium phosphate pyrolytic process, add sodium hydroxide solution,, can improve energy consumption simultaneously, increase cost for wastewater treatment though can improve the release rate of ammonia nitrogen.
" the Repeated used of MAP decomposition residues for the removal of high ammonium concentration from landfill leachate " that Shilong He etc. delivered in " Chemosphere " 66 phases in 2007; When utilizing magnesium ammonium phosphate pyrolysis product circular treatment percolate; For the first time ammonia nitrogen removal frank reaches 84%, the six time and then reduces to 62%." the Removal of ammonia as struvite from anaerobic digester effluents and recycling of magnesium and phosphate " that Mustafa T rker etc. delivered in " Bioresource Technology " 98 phases in 2007; When utilizing magnesium ammonium phosphate pyrolysis product circular treatment anaerobism supernatant; For the first time ammonia nitrogen removal frank reaches 92%, the five time and then reduces to 77%.In the heavy ammonia process of magnesium ammonium phosphate circulation, along with the increase of cycle index, obviously descending appears in ammonia nitrogen removal frank." Removal of aqueous ammonium with magnesium phosphates obtained from the ammonium-elimination of magnesium ammonium phosphate " that Shigeru Sugiyama etc. delivered in " Journal of Colloid and Interface Science " 292 phases in 2005 thinks; In the magnesium ammonium phosphate pyrolytic process; Be attended by the generation of magnesium pyrophosphate verivate, and the heavy ammonia poor ability of magnesium pyrophosphate.Along with the increase of cycle index, magnesium pyrophosphate content progressively rises, and causes ammonia nitrogen removal frank along with the increase of cycle index obviously descends.Up to now, do not see the relevant report that solves this difficult problem as yet.
Summary of the invention
The problem that solves
Remove the problem that the ammonia nitrogen cost is high in the waste water, clearance is not high to ammoniomagnesium phosphate crystal method in the prior art; The invention provides the method that a kind of chemicrystallization method reclaims ammonia nitrogen in the waste water; It can effectively solve the too high problem of ammoniomagnesium phosphate crystal method reagent cost, has solved the difficult problem along with the increase ammonia nitrogen removal frank decline of the heavy ammonia number of times of magnesium ammonium phosphate circulation simultaneously.
Technical scheme
Inventive principle: prefabricated magnesium ammonium phosphate crystal, oven dry adds sodium hydroxide powder in the magnesium ammonium phosphate crystal after oven dry; Grind evenly, regulate the mol ratio of magnesium ammonium phosphate and sodium hydroxide, control pyrolysis temperature, time; The ammonia that pyrolysis produces reclaims through acid solution, and pyrolysis product drops into the heavy ammonia of waste water, reclaims the heavy ammonia of magnesium ammonium phosphate solid circulation; Increase the acidolysis program in the magnesium ammonium phosphate pyrolysis working cycle, control pH, acidolysis time and acidolysis temperature, the heavy ammonia of acid hydrolysate circulation.
A kind of chemicrystallization method reclaims the method for ammonia nitrogen in the waste water, the steps include:
(1) in the magnesium ammonium phosphate solid, add sodium hydroxide powder, sodium hydroxide: the magnesium ammonium phosphate mass ratio is 20:245 ~ 120:245, then at 80 ℃ ~ 190 ℃ following pyrolysis 1 h ~ 5 h, gets pyrolysis product, and the ammonia that pyrolysis simultaneously produces adopts acid solution to reclaim;
(2) in waste water, add the pyrolysis product that step (1) makes, pyrolysis product (calculating with sodium phosphate magnesium): the ammonia nitrogen mass ratio is 142:17 in the waste water, and the ammonia nitrogen in pyrolysis product and the waste water forms the magnesium ammonium phosphate crystal, precipitates and separates with waste water;
(3) the magnesium ammonium phosphate crystal in the recovering step (2); Oven dry; Then with sodium hydroxide: the magnesium ammonium phosphate crystal is that the mass ratio of 20:245 ~ 120:245 adds sodium hydroxide powder, and thermal degradation 1 h ~ 5 h under 80 ℃ ~ 190 ℃ temperature are decomposed into sodium phosphate magnesium; By product magnesium pyrophosphate and trimagnesium phosphate drop into the heavy ammonia of waste water circulation with degradation production;
(4) after the every circulation in described step (1)-(3) 2 ~ 5 times; With carrying out acidolysis in the pyrolysis product in the step (3) (sodium phosphate magnesium, magnesium pyrophosphate and trimagnesium phosphate) the input acidic solution; Acidolysis 1 ~ 5 h under 80 ℃ ~ 120 ℃ temperature; Acid hydrolysate solution, acid hydrolysate solution (secondary magnesium phosphate solution) and waste water be that the mol ratio of 1:1 drops in the waste water circulation and sinks ammonia with (ammonia nitrogen in the waste water).
Preferably, the acidic solution described in the step (4) is one or both in sulfuric acid or the hydrochloric acid, and the pH of acidic solution is 1 ~ 5.
Preferably, magnesium ammonium phosphate and sodium hydroxide in the said step (1), sodium hydroxide: magnesium ammonium phosphate mass ratio 40:245 ~ 80:245.
Preferably, pyrolysis temperature is 100 ℃ ~ 110 ℃ in the said step (1).
Preferably, pyrolysis time is 2 ~ 3 h in the said step (1).
Preferably, the acidolysis temperature of said step (4) is 110 ℃ ~ 120 ℃.
Preferably, the acidolysis time of said step (4) is 2 ~ 3 h.
Preferably, the acidolysis pH of said step (4) is 1 ~ 2.
Beneficial effect
Than known prior art, the invention has the advantages that:
(1) the present invention adopts the technical scheme of the heavy ammonia of magnesium ammonium phosphate pyrolysis product circulation; Not only reduced the reagent cost of the heavy ammonia of ammoniomagnesium phosphate crystal method; And, through in the magnesium ammonium phosphate pyrolytic process, adding sodium hydroxide powder, improved the release rate of magnesium ammonium phosphate pyrolysis ammonia nitrogen; In the working cycle; Increase the acidolysis step, can discharge the by product magnesium pyrophosphate and mg ion and the phosphoric acid salt in the trimagnesium phosphate that generate in the pyrolytic process, efficiently solve problem along with the heavy ammonia rate decline of the increase of the heavy ammonia cycle index of magnesium ammonium phosphate pyrolysis product;
(2) magnesium ammonium phosphate is in adding the pyrolytic process of sodium hydroxide powder, sodium hydroxide: the magnesium ammonium phosphate mass ratio is that 20:245 ~ 120:245, pyrolysis temperature are that 80 ℃ ~ 190 ℃, pyrolysis time are 1 ~ 5 h, and ammonia-nitrogen removal rate is 89% ~ 100%; The input ratio of pyrolysis temperature, pyrolysis time and sodium hydroxide and magnesium ammonium phosphate are released being proportionate property of ammonia rate; Along with rising or the prolongation of pyrolysis time and the increase of sodium hydroxide ratio of pyrolysis temperature, magnesium ammonium phosphate ammonia nitrogen release rate progressively rises, and uses for cutting down the consumption of energy, save medicament expense; Obtain higher ammonia nitrogen release rate simultaneously; Known by experimental result, work as sodium hydroxide: the magnesium ammonium phosphate mass ratio is that 40:245 ~ 80:245, pyrolysis temperature are that 100 ℃ ~ 110 ℃, pyrolysis time are 2 ~ 3 h, and the ammonia nitrogen release rate reaches 96%; Experiment shows that the ratio that continues to improve pyrolysis temperature or prolongation pyrolysis time and increase sodium hydroxide all is uneconomic;
(3) in the magnesium ammonium phosphate pyrolytic process, except that generating principal product sodium phosphate magnesium, also be attended by the generation of magnesium pyrophosphate; And in the working cycle of magnesium ammonium phosphate pyrolysis product, can be attended by the generation of trimagnesium phosphate, and the heavy ammonia poor of magnesium pyrophosphate and trimagnesium phosphate; Increase along with the pyrolysis cycle index; The heavy ammonia performance of pyrolysis product progressively descends, and major cause is that the accumulation of magnesium pyrophosphate and trimagnesium phosphate causes, in the technical scheme of the present invention through the acidolysis step; Be discharged into magnesium in magnesium pyrophosphate and the trimagnesium phosphate and phosphoric acid salt in the solution with mg ion and phosphatic form, improve heavy ammonia effect;
(4) in the step of the present invention (4), the pH of acidic solution is 1 ~ 5, acidolysis temperature is that 80 ℃ ~ 120 ℃, acidolysis time are 1 ~ 5 h, and the transformation efficiency of pyrophosphate salt is 5% ~ 89%; Know that by experimental result the transformation efficiency of pyrophosphate salt and pH value are negative correlation, but with acidolysis temperature and being proportionate property of acidolysis time; Along with the pH value reduces, the pyrophosphate salt transformation efficiency increases, and along with the raising or the prolongation of acidolysis time of acidolysis temperature; The pyrophosphate salt transformation efficiency is also in rising trend; When the pH of acidic solution is 1 ~ 2, acidolysis temperature is that 110 ℃ ~ 120 ℃, acidolysis time are 2 ~ 3 h, the transformation efficiency of tetra-sodium hydrochlorate can reach 82%, promptly higher transformation efficiency; Because in the magnesium ammonium phosphate pyrolysis working cycle; The content of magnesium pyrophosphate and trimagnesium phosphate is in a lower level, takes all factors into consideration the double factor of economy and transformation efficiency, above-mentioned conditionally complete can rejected heat hydrolysis products magnesium pyrophosphate and trimagnesium phosphate in mg ion and phosphoric acid salt.
Description of drawings
Fig. 1 is a magnesium ammonium phosphate pyrolysis cycle diagram;
Fig. 2 removes the ammonia nitrogen design sketch in the coking chemical waste water for the heavy ammonia process of magnesium ammonium phosphate pyrolysis product circulation;
Fig. 3 removes the ammonia nitrogen design sketch in the breeding wastewater for the heavy ammonia process of magnesium ammonium phosphate pyrolysis product circulation;
Fig. 4 removes the ammonia nitrogen design sketch in the fertilizer industry waste water for the heavy ammonia process of magnesium ammonium phosphate pyrolysis product circulation.
Embodiment
Further introduce the present invention below in conjunction with accompanying drawing and concrete embodiment.
Embodiment 1
Get coking chemical waste water, waste water quality is seen table 1.
Table 1 coking chemical waste water water quality
| Parameter | Unit | Concentration |
| COD | mg/L | 220±10 |
| pH | - | 7.2±0.1 |
| NH 4-N | mg/L | 650±20 |
| BOD | mg/L | 50±1 |
| Ca 2+ | mg/L | 21±0.5 |
A kind of chemicrystallization method of present embodiment reclaims the method for ammonia nitrogen in the waste water, the steps include:
(1) prefabricated magnesium ammonium phosphate crystal; In the magnesium ammonium phosphate solid, add sodium hydroxide powder and carry out pyrolysis; Sodium hydroxide: the magnesium ammonium phosphate mass ratio is that 40:245, pyrolysis temperature are that 110 ℃, pyrolysis time are 3 h, and it is that 2% sulphuric acid soln reclaims that the ammonia that pyrolysis simultaneously produces adopts massfraction;
(2) pyrolysis product that makes step (1) adds in the waste water of table 1; Wherein, pyrolysis product (calculating with sodium phosphate magnesium): the ammonia nitrogen mass ratio is 142:17 in the waste water, sinks ammonia; Ammonia nitrogen in pyrolysis product and the waste water forms the magnesium ammonium phosphate crystal, and deposition is also separated with waste water;
(3) the magnesium ammonium phosphate crystal in the recovering step (2); Oven dry; Then with sodium hydroxide: the magnesium ammonium phosphate crystal mass is than being that 40:245 adds sodium hydroxide powder, and thermal degradation 5h under 85 ℃ of temperature is decomposed into sodium phosphate magnesium; By product magnesium pyrophosphate and trimagnesium phosphate drop into the heavy ammonia of waste water circulation with degradation production;
(4) after the every circulation in described step (1)-(3) 3 times, the pyrolysis product in the step (3) dropped in the sulphuric acid soln carry out acidolysis, acidolysis condition is: the pH of acidic solution is 1, acidolysis temperature is that 120 ℃, acidolysis time are 3 h; With
(ammonia nitrogen in the waste water) mol ratio the heavy ammonia of circulation in the waste water of ratio input table 1 of 1:1 acid hydrolysate (secondary magnesium phosphate solution), the recycling precipitate recycle.
Fig. 1 is seen in magnesium ammonium phosphate (being called for short MAP) pyrolysis working cycle.Along with the increase of number of times, the heavy ammonia process of magnesium ammonium phosphate pyrolysis product circulation is removed coking chemical waste water ammonia nitrogen effect and is seen Fig. 2.Can see that from figure the heavy ammonia rate of magnesium ammonium phosphate pyrolysis product circulation remains on more than 85%, along with the increase of cycle index, heavy ammonia rate changes not obvious.
Through method of the present invention; The medicament expense that not only greatly reduces magnesium ammonium phosphate method treatment of high concentration ammonia nitrogen waste water is used; And kept a higher ammonia nitrogen removal effect; Ammonia nitrogen in waste water content after the processing makes things convenient for the subsequent disposal of waste water at 93.5 mg/L, but precipitated product recycling also simultaneously.
Embodiment 2
Get breeding wastewater, waste water quality is seen table 2.
Table 2 breeding wastewater water quality
| Parameter | Unit | Concentration |
| COD | mg/L | 550±10 |
| pH | - | 7.4±0.1 |
| NH 4-N | mg/L | 860±20 |
| BOD | mg/L | 90±10 |
| TOC | mg/L | 120±10 |
A kind of chemicrystallization method of present embodiment reclaims the method for ammonia nitrogen in the waste water, the steps include:
(1) prefabricated magnesium ammonium phosphate crystal; In the magnesium ammonium phosphate solid, add sodium hydroxide powder; Sodium hydroxide: the magnesium ammonium phosphate mass ratio is that 80:245, pyrolysis temperature are that 100 ℃, pyrolysis time are 2 h, and it is that 2% sulphuric acid soln reclaims that the ammonia that pyrolysis simultaneously produces adopts massfraction;
(2) in the breeding wastewater of table 2, add the pyrolysis product that step (1) makes; Pyrolysis product (calculating with sodium phosphate magnesium): the ammonia nitrogen mass ratio is 142:17 in the waste water; Ammonia nitrogen in pyrolysis product and the waste water forms the magnesium ammonium phosphate crystal, and deposition is also separated with waste water;
(3) the magnesium ammonium phosphate crystal in the recovering step (2); Oven dry; Then with sodium hydroxide: the magnesium ammonium phosphate crystal mass at 80 ℃ of following thermal degradation 1 h, is decomposed into sodium phosphate magnesium than being that 20:245 adds sodium hydroxide powder; By product magnesium pyrophosphate and trimagnesium phosphate drop into the heavy ammonia of circulation in the breeding wastewater with degradation production;
(4) after the every circulation in described step (1)-(3) 5 times; Pyrolysis product in the step (3) (sodium phosphate magnesium, magnesium pyrophosphate and trimagnesium phosphate) dropped in the sulphuric acid soln carry out acidolysis, acidolysis condition is: the pH of acidic solution is 2, acidolysis temperature is that 110 ℃, acidolysis time are 2 h; Acid hydrolysate solution (secondary magnesium phosphate solution) is the heavy ammonia of circulation in the breeding wastewater of ratio input table 2 of 1:1 with
(ammonia nitrogen in the waste water) mol ratio, the recycling precipitate recycle.
Fig. 1 is seen in magnesium ammonium phosphate (being called for short MAP) pyrolysis working cycle.Along with the increase of number of times, the ammonia nitrogen effect that the heavy ammonia of magnesium ammonium phosphate pyrolysis product circulation is removed in the breeding wastewater is seen Fig. 3.Can see that from figure the heavy ammonia rate of magnesium ammonium phosphate pyrolysis product circulation remains on more than 82%, along with the increase of cycle index, heavy ammonia rate changes not obvious.
Through method of the present invention; The medicament expense that not only greatly reduces magnesium ammonium phosphate method treatment of high concentration ammonia nitrogen waste water is used; And kept a higher ammonia nitrogen removal effect; Breeding wastewater ammonia-nitrogen content after the processing makes things convenient for the subsequent disposal of waste water at 115.3 mg/L, but precipitated product recycling also simultaneously.
Embodiment 3
Get fertilizer industry waste water, waste water quality is seen table 1.
Table 3 fertilizer industry waste water quality
| Parameter | Unit | Concentration |
| COD | mg/L | 560±10 |
| pH | - | 7.86±0.1 |
| NH 4-N | mg/L | 1197±20 |
| SS | mg/L | 10±1 |
| Mg 2+ | mg/L | 0.516±0.1 |
A kind of chemicrystallization method of present embodiment reclaims the method for ammonia nitrogen in the waste water, the steps include:
(1) prefabricated magnesium ammonium phosphate crystal; In the magnesium ammonium phosphate solid, add sodium hydroxide powder; Sodium hydroxide: the magnesium ammonium phosphate mass ratio is that 60:245, pyrolysis temperature are that 105 ℃, pyrolysis time are 2.5 h, and it is that 2% sulphuric acid soln reclaims that the ammonia that pyrolysis simultaneously produces adopts massfraction;
(2) pyrolysis product that makes step (1) adds in the fertilizer industry waste water of table 3; Wherein, Pyrolysis product (calculating with sodium phosphate magnesium): the ammonia nitrogen mass ratio is 142:17 in the waste water; Sink ammonia, the ammonia nitrogen in pyrolysis product and the waste water forms the magnesium ammonium phosphate crystal, and deposition is also separated with waste water;
(3) the magnesium ammonium phosphate crystal in the recovering step (2); Oven dry; Then with sodium hydroxide: the magnesium ammonium phosphate crystal mass is than being that 120:245 adds sodium hydroxide powder, and thermal degradation 3 h are decomposed into sodium phosphate magnesium under 190 ℃ of temperature; By product magnesium pyrophosphate and trimagnesium phosphate drop into the heavy ammonia of waste water circulation with degradation production;
(4) after the every circulation in described step (1)-(3) 2 times, drop into step (3) pyrolysis product in the hydrochloric acid soln and to carry out acidolysis, acidolysis condition is: the pH of hydrochloric acid soln is 1.5, acidolysis temperature is that 115 ℃, acidolysis time are 2.5 h; With
(ammonia nitrogen in the waste water) mol ratio the heavy ammonia of circulation in ratio input table 3 waste water of 1:1 acid hydrolysate solution (secondary magnesium phosphate solution), the recycling precipitate recycle.
Fig. 1 is seen in magnesium ammonium phosphate (being called for short MAP) pyrolysis working cycle.The heavy ammonia of magnesium ammonium phosphate pyrolysis product circulation is removed fertilizer industry ammonia nitrogen in waste water effect and is seen Fig. 4.Can see that from figure the heavy ammonia rate of magnesium ammonium phosphate pyrolysis product circulation remains on more than 80%, along with the increase of cycle index, heavy ammonia rate changes not obvious.
Through method of the present invention; The medicament expense that not only greatly reduces magnesium ammonium phosphate method treatment of high concentration ammonia nitrogen waste water is used; And kept a higher ammonia nitrogen removal effect; Ammonia nitrogen in waste water content after the processing makes things convenient for the subsequent disposal of waste water at 141.9 mg/L, but precipitated product recycling also simultaneously.
According to embodiment 1 ~ 3; Add sodium hydroxide powder in the magnesium ammonium phosphate pyrolytic process, effectively improved the ammonia rate of releasing of magnesium ammonium phosphate, according to the method for the invention; The releasing the ammonia rate and can reach more than 96% of magnesium ammonium phosphate; In working cycle, increase the acidolysis program, efficiently solve along with cycle index increases, the magnesium ammonium phosphate pyrolysis product is handled the difficult problem that heavy ammonia rate descends in the waste water process.
Claims (8)
1. a chemicrystallization method reclaims the method for ammonia nitrogen in the waste water, the steps include:
(1) in the magnesium ammonium phosphate solid, add sodium hydroxide powder, sodium hydroxide: the magnesium ammonium phosphate mass ratio is 20:245 ~ 120:245, then at 80 ℃ ~ 190 ℃ following pyrolysis 1 h ~ 5 h, gets pyrolysis product, and the ammonia that pyrolysis simultaneously produces adopts acid solution to reclaim;
(2) in waste water, add the pyrolysis product that step (1) makes, pyrolysis product: the ammonia nitrogen mass ratio is 142:17 in the waste water, and ammonia nitrogen in pyrolysis product and the waste water forms the magnesium ammonium phosphate crystal, and deposition is also separated with waste water;
(3) the magnesium ammonium phosphate crystal in the recovering step (2); Oven dry; Then with sodium hydroxide: the magnesium ammonium phosphate crystal is that the mass ratio of 20:245 ~ 120:245 adds sodium hydroxide powder, and thermal degradation 1 h ~ 5 h under 80 ℃ ~ 190 ℃ temperature, degradation production drop into the heavy ammonia of waste water circulation;
(4) after the every circulation in described step (1)-(3) 2 ~ 5 times; With carrying out acidolysis in the input of the pyrolysis product in the step (3) acidic solution; Acidolysis 1 ~ 5 h under 80 ℃ ~ 120 ℃ temperature; Get acid hydrolysate solution, acid hydrolysate solution and waste water are that the mol ratio of 1:1 drops into the heavy ammonia of circulation in the waste water with
.
2. a kind of chemicrystallization method according to claim 1 reclaims the method for ammonia nitrogen in the waste water, it is characterized in that the acidic solution described in the step (4) is one or both in sulfuric acid or the hydrochloric acid, and the pH of acidic solution is 1 ~ 5.
3. a kind of chemicrystallization method according to claim 1 reclaims the method for ammonia nitrogen in the waste water, it is characterized in that sodium hydroxide in the said step (1): magnesium ammonium phosphate mass ratio 40:245 ~ 80:245.
4. according to the method for ammonia nitrogen in claim 1 or the 3 described a kind of chemicrystallization methods recovery waste water, it is characterized in that pyrolysis temperature is 100 ℃ ~ 110 ℃ in the said step (1).
5. a kind of chemicrystallization method according to claim 4 reclaims the method for ammonia nitrogen in the waste water, it is characterized in that, pyrolysis time is 2 ~ 3 h in the said step (1).
6. a kind of chemicrystallization method according to claim 5 reclaims the method for ammonia nitrogen in the waste water, it is characterized in that the acidolysis temperature of said step (4) is 110 ℃ ~ 120 ℃.
7. a kind of chemicrystallization method according to claim 6 reclaims the method for ammonia nitrogen in the waste water, it is characterized in that the acidolysis time of said step (4) is 2 ~ 3 h.
8. according to the method for ammonia nitrogen in claim 2 or the 7 described a kind of chemicrystallization methods recovery waste water, it is characterized in that the acidolysis pH of said step (4) is 1 ~ 2.
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